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EP1866259B1 - Zementzusatzmittel - Google Patents

Zementzusatzmittel Download PDF

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Publication number
EP1866259B1
EP1866259B1 EP06731128A EP06731128A EP1866259B1 EP 1866259 B1 EP1866259 B1 EP 1866259B1 EP 06731128 A EP06731128 A EP 06731128A EP 06731128 A EP06731128 A EP 06731128A EP 1866259 B1 EP1866259 B1 EP 1866259B1
Authority
EP
European Patent Office
Prior art keywords
monomer
group
cement
acid
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
EP06731128A
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English (en)
French (fr)
Other versions
EP1866259A4 (de
EP1866259A1 (de
Inventor
Hiroshi Yamazaki
Tsuyoshi Hirata
Akihiko Yamashita
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Shokubai Co Ltd
Original Assignee
Nippon Shokubai Co Ltd
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Publication of EP1866259A4 publication Critical patent/EP1866259A4/de
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Publication of EP1866259B1 publication Critical patent/EP1866259B1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/005—Modified block copolymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/308—Slump-loss preventing agents

Definitions

  • the present invention relates to a cement admixture. More specifically, the present invention relates to a cement admixture containing two or more members of polycarboxylic acid-based polymers having a specific constitutional unit.
  • a cement admixture containing a polycarboxylic acid-based polymer has been widely used in a cement composition such as cement paste, mortar, concrete, and the like, and is now indispensable material to build structure of civil engineering and construction, and the like from a cement composition.
  • a cement admixture is used as a water-reducing agent, and serves to improve strength or durability of hardened material, by enhancing fluidity of a cement composition and reducing water content of the cement composition.
  • a polycarboxylic acid-based water-reducing agent having a polycarboxylic acid-based polymer as a main component which fulfills higher water-reducing performance as compared with a conventional naphthalene-based water-reducing agent, has had many practical application results as a high performance AE water-reducing agent.
  • a copolymer of unsaturated carboxylic acid and a vinyl ether-based monomer has been utilized in various fields such as a cement dispersing agent and a builder for a detergent.
  • JP-A-9-309756 discloses the use of a copolymer of a vinyl ether-based monomer and maleic anhydride as a cement admixture.
  • US-B-6777517 and WO 2004/087602 disclose a method for producing a copolymer of a vinyl ether-based monomer and unsaturated carboxylic acid. The method, however, can not provide a highly pure copolymer while suppressing side reactions.
  • EP 0556061 discloses a cement admixture composition formed from an alkenyl ether/maleic anhydride copolymer.
  • EP0520602 discloses a concrete composition comprising a hydraulic cement material, water, fine aggregate, coarse aggregate and a copolymer component comprising an alkenyl ether/maleic anhydride copolymer.
  • JP 2003 - 221266 discloses a cement admixture comprising a copolymer having a unit derived from an unsaturated (poly)alkylene glycol ether-based monomer and a unit derived from an unsaturated polyalkylene glycol ether-based monomer and a unit derived from an unsaturated monocarboxylic acid-based monomer.
  • JP 2002 - 003259 discloses a cement dispersing agent consisting of a copolymer mixture obtained by copolymerizing an unsaturated carboxylic acid derivative and (meth) acrylic acid and a copolymer mixture obtained by copolymerizing an alkenyl ether monomer and maleic acid or maleic anhydride.
  • JP 9 - 28 66 47 discloses an additive composition containing a copolymer comprising a polyoxyalkylene, sulfonic acid and maleic acid and a copolymer containing a polyoxyalkylene.
  • JP 5-306152 discloses a cement dispersant composition comprising a copolymer of maleic anhydride/alkenyl ether and a copolymer of alkenyl ether/maleic anhydride.
  • JP 2003-335562 discloses a water reducing agent for cement comprising a copolymer and its salt.
  • the present invention has been made in view of such circumstances and aims at providing a cement admixture having superior water-reducing performance, along with no decrease in slump and slump flow caused by decrease in fluidity of a cement composition over time.
  • the present inventors have found, after comprehensive study on various cement admixtures, that a cement admixture having as essential components a polycarboxylic acid-based polymer (A) having essentially a structure derived from a vinyl ether-based monomer, and a polycarboxylic acid-based polymer (B) having a polyalkylene glycol chain with carbon atoms of 2 to 18 and having a structure different from that of a polycarboxylic acid-based polymer (A), was useful to obtain a cement composition having superior water-reducing performance, along with no decrease in slump and slump flow caused by decrease in fluidity of a cement composition over time. On the basis of this knowledge, the present invention has been attained.
  • a cement admixture comprising two or more members of polycarboxylic acid-based polymers, wherein the cement admixture comprises at least one polycarboxylic acid-based polymer (A) having a constitutional unit represented by the following formula (1) : wherein R 1 and R 2 independently represent a hydrogen atom, an alkyl group with carbon atoms of 1 to 30, an alkenyl group with carbon atoms of 1 to 30, an aryl group with carbon atoms of 6 to 12; A represents an alkylene group with carbon atoms of 1 to 30 or an arylene group with carbon atoms of 6 to 12; a is 0 or 1; OR 3 represents an oxyalkylene group with carbon atoms of 2 to 18, wherein each OR 3 may be the same or different to each other, provided that when OR 3 is in a mixed form of two or more members, each OR 3 may be added in a block or random form; R 4 represents a hydrogen atom or a hydrocarbon group with carbon atoms
  • n is in the range of 1 to 10.
  • OR 7 is represented by the following formula (3): wherein R 9 represents an alkylene group with carbon atoms of 3 to 18; o and q independently represent an average mole number of oxyalkylene groups added and is in the range of 0 to 200, provided that when either one of o or q is 0, the other is in the range of 1 to 200; p represents an average mole number of oxyalkylene groups added and is in the range of 1 to 50; and the total of number of o, p and q (o+p+q), is in the range of 2 to 300.
  • the cement admixture of the present invention has a composition as described above and thus fulfills superior cement dispersing performance and water-reducing performance, and can suitably be applied to various cement compositions.
  • the cement admixture can also provide easy work at the field handling thereof due to showing little decrease in slump and slump flow caused by decrease in fluidity of a cement composition over time. Accordingly, by using the cement admixture of the present invention, work efficiency, and the like can be improved in building structure of civil engineering and construction. Further, the use of the cement admixture can provide significant economic merits, because of only the small amount of a cement admixture added is required to attain such effects.
  • a cement admixture comprising two or more members of polycarboxylic acid-based polymers, wherein the cement admixture comprises at least one polycarboxylic acid-based polymer (A) having a constitutional unit represented by the following formula (1) : wherein R 1 and R 2 independently represent a hydrogen atom, an alkyl group with carbon atoms of 1 to 30, an alkenyl group with carbon atoms of 1 to 30, an aryl group with carbon atoms of 6 to 12; A represents an alkylene group with carbon atoms of 1 to 30 or an arylene group with carbon atoms of 6 to 12; a is 0 or 1; OR 3 represents an oxyalkylene group with carbon atoms of 2 to 18, wherein each OR 3 may be the same or different to each other, provided that when OR 3 is in a mixed form of two or more members, each OR 3 may be added in a block or random form; R 4 represents a hydrogen atom or a hydrocarbon group with carbon atoms of 1 to 30; and m
  • the polycarboxylic acid-based polymer (A) as one of the essential components in the present invention is a polymer having two or more carboxyl groups or salts thereof in its molecule, and having a specific structure represented by the formula (1) introduced as a constitutional unit of the polymer.
  • the polycarboxylic acid-based polymer (B) as the other essential component in the present invention is a polymer having two or more carboxyl groups or salts thereof in its molecule, and having a specific structure represented by the formula (2) introduced as a constitutional unit of the polymer.
  • the polycarboxylic acid-based polymer (B) is preferably a polymer having two or more carboxyl groups or salts thereof in its molecule, and having a specific structure represented by the formula (2) wherein n is in the range of 1 to 10, and/or a specific structure represented by the formula (2) wherein at least a part of OR 7 in the formula (2) is represented by the following formula (3), which is explained in detail below, introduced as a constitutional unit of the polymer.
  • the weight ratio of the polycarboxylic acid-based polymer (A) and the polycarboxylic acid-based polymer (B) [weight ratio of (A)/(B)] is an arbitrary one within the range of 1/99 to 99/1.
  • a cement admixture of the present invention preferably contains the polycarboxylic acid-based polymer (B) in a larger amount than the polycarboxylic acid-based polymer (A).
  • a cement admixture of the present invention preferably contains the polycarboxylic acid-based polymer (A) in a relatively larger amount than the polycarboxylic acid-based polymer (B).
  • the weight ratio of the polycarboxylic acid-based polymer (A) and the polycarboxylic acid-based polymer (B) [weight ratio of (A) / (B) ] is preferably in the range of 50/50 to 1/99, more preferably 40/60 to 1/99, and most preferably 30/70 to 1/99.
  • the weight ratio of the polycarboxylic acid-based polymer (A) and the polycarboxylic acid-based polymer (B) [weight ratio of (A) / (B) ] is preferably in the range of 10/90 to 99/1, more preferably 20/80 to 99/1 and most preferably 30/70 to 99/1.
  • the cement admixture of the present invention may be composed of only the polycarboxylic acid-based polymer (A) and the polycarboxylic acid-based polymer (B), or alternatively in addition to the polycarboxylic acid-based polymers (A) and (B), other components may be contained.
  • a cement admixture of the present invention is most preferably composed of only polycarboxylic acid-based polymers (A) and (B), i.e., the total weight ratio of the polycarboxylic acid-based polymer (A) and the polycarboxylic acid-based polymer (B), occupying the total weight of a cement admixture, is most preferably 100% by weight.
  • the total weight ratio of the polycarboxylic acid-based polymer (A) and the polycarboxylic acid-based polymer (B), occupying the total weight of a cement admixture of the present invention is not especially limited as long as it is such ratio as fulfills the desired effects (for example, superior water-reducing performance, along with effects of suppressing and preventing the decrease in slump value and slump flow value over time). It is preferably not lower than 50% by weight, further preferably not lower than 60% by weight, most preferably not lower than 70% by weight, and particularly most preferably not lower than 80% by weight.
  • a polycarboxylic acid-based polymer (A), as a component of a cement admixture, has a constitutional unit derived from a monomer having a carboxyl group or the salt thereof in its molecule, and a constitutional unit represented by the following formula (1):
  • R 1 and R 2 represent a hydrogen atom, an alkyl group with carbon atoms of 1 to 30, an alkenyl group with carbon atoms of 1 to 30, or an aryl group with carbon atoms of 6 to 12.
  • R 1 and R 2 may be the same as or different to each other.
  • alkyl group with carbon atoms of 1 to 30 is not especially limited, and may be, for example, straight and branched chain alkyl groups having carbon atoms of 1 to 30 such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isooctyl, 2,3,5-trimethylhexyl, 4-ethyl-5-methyloctyl, 2-ethylhexyl, tetradecyl, octadecyl, and icosyl; cycloalkyl groups such as cyclobutyl, cyclopentyl, cyclohexyl, cyclohepty
  • An aryl group with carbon atoms of 6 to 12 is not especially limited and for example, phenyl, benzyl, phenethyl, o-, m- or p-tolyl, 2,3- or 2,4-xylyl, mesityl, naphthyl, and the like.
  • R 1 and R 2 are preferably a hydrogen atom and a methyl group, and more preferably a hydrogen atom.
  • A represents an alkylene group with carbon atoms of 1 to 30 or an arylene group with carbon atoms of 6 to 12.
  • an alkylene group with carbon atoms of 1 to 30 is not especially limited, and may be, for example, straight or branched chain alkylene groups with carbon atoms of 1 to 30 such as methylene, ethylene, trimethylene, tetramethylene, propylene, butylene, and the like.
  • an arylene group with carbon atoms of 6 to 12 is not especially limited, and may be, for example, o-, m-, p-phenylene, 1,2-, 1,4-naphthylene, and the like.
  • a is 0 or 1.
  • OR 3 represents an oxyalkylene group with carbon atoms of 2 to 18, preferably an oxyalkylene group with carbon atoms of 2 to 8 and more preferably an oxyalkylene group with carbon atoms of 2 to 4.
  • an oxyalkylene group oxyethylene group, oxypropylene group, oxybutylene group, oxyisobutylene group, oxystyrene group, and the like may be preferably included.
  • OR 3 represents an oxyethylene group, oxypropylene group or oxybutylene group, and further more preferably, an oxyethylene group or oxypropylene group.
  • these oxyalkylene groups are present in plural in one constitutional unit (namely, m in the formula (2) is 2 or more), they may be present singly or in a mixed form of two or more members in one constitutional unit. In the case when two or more members of oxyalkylene groups are present, theymay take any form of a random addition, ablockaddition, analternateaddition, and the like.
  • m represents an average mole number of oxyalkylene groups added and is in the range of 1 to 300. The number, m, over 300 would provide high viscosity and worsen workability.
  • m is in the range of 1 to 200, more preferably 5 to 100, further preferably 10 to 60, and most preferably 15 to 40.
  • R 4 represents a hydrogen atom or a hydrocarbon group with carbon atoms of 1 to 30, preferably a hydrogen atom or a hydrocarbon group with carbon atoms of 1 to 20, more preferably a hydrogen atom or a hydrocarbon group with carbon atoms of 1 to 18, and particularly preferably a hydrogen atom or a hydrocarbon group with carbon atoms of 1 to 12.
  • hydrocarbon group specifically, straight or branched chain alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isooctyl, 2,3,5-trimethylhexyl, 4-ethyl-5-methyloctyl, 2-ethylhexyl, tetradecyl, octadecyl, and icosyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; aryl group such as
  • a constitutional unit represented by the formula (1) is derived from a monomer (a) represented by the following formula (4).
  • R 1 , R 2 , R 3 , R 4 , A, a, and m are as defined in the formula (1).
  • a polycarboxylic acid-based polymer (A), an essential component according to the present invention may be any polymer as long as it has a constitutional unit represented by the formula (1), and a constitutional unit derived from a monomer having a carboxyl group or the salt thereof in its molecule, as described in detail below, and a synthesis route thereof is not limited.
  • the following route can be used.
  • a polycarboxylic acid-based polymer (A) can be obtained by polymerization of a single or two or more monomers having a carboxyl group or the salt thereof and a polymerizable double bond in its molecule, and a single or two or more monomers (a) represented by the formula (4).
  • the monomer (a) is not especially limited, as long as it has a structure represented by the formula (4).
  • a so-called vinyl-based monomer can be included.
  • a vinyl ether-based monomer represented by the formula (4) wherein OR 4 is an OH group and obtained by the addition of an alkylene oxide to a vinyl alcohol, or a vinyl-based monomer represented by the formula (4) wherein OR 4 is an OCH 3 group and obtained by the addition of methoxypolyalkylene oxide to acetylene can be included.
  • a polycarboxylic acid-based polymer (B), as a component of a cement admixture, has a constitutional unit derived from a monomer having two or more carboxyl groups and salts thereof in its molecule, and a constitutional unit represented by the following formula (2).
  • R 5 and R 6 represent a hydrogen atom or a methyl group. In this case R 5 and R 6 may be the same as or different to each other.
  • x represents the number of a methylene (-CH 2 -) unit present in one constitutional unit of the formula (2), and is an integer in the range of 0 to 2, preferably an integer of 0 to 1, and more preferably 0.
  • y represents the number of a carbonyl (-CO-) unit present in one constitutional unit of the formula (2), and is 1.
  • R 8 represents a hydrogen atom or a hydrocarbon group with carbon atoms of 1 to 30, preferably a hydrogen atom or a hydrocarbon group with carbon atoms of 1 to 20, more preferably a hydrogen atom or a hydrocarbon group with carbon atoms of 1 to 18, and particularly preferably a hydrogen atom or a hydrocarbon group with carbon atoms of 1 to 12.
  • hydrocarbon group specifically, straight or branched chain alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isooctyl, 2,3,5-trimethylhexyl, 4-ethyl-5-methyloctyl, 2-ethylhexyl, tetradecyl, octadecyl, and icosyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; aryl groups such as
  • n represents an average mole number of oxyalkylene groups (OR 7 ) added and is a number in the range of 1 to 300. If n, the average mole number of oxyalkylene groups (OR 7 ) added, is relatively small, the adsorption rate of a polycarboxylic acid-based polymer (B) to cement would become relatively slow, by which a polycarboxylic acid-based polymer (B) can effectively act on cement even after certain time passes. Therefore, in the case to effectively suppress and prevent, in particular, decrease in slump and slump flow caused by decrease in fluidity of a cement composition over time, n is preferably in the range of 1 to 100, more preferably 1 to 50, further preferably 1 to 25, and most preferably 1 to 10.
  • n is preferably in the range of 6 to 300, more preferably 10 to 300, further preferably 25 to 300, and most preferably 75 to 300.
  • OR 7 represents an oxyalkylene group with carbon atoms of 2 to 18, preferably an oxyalkylene group with carbon atoms of 2 to 8, and more preferably an oxyalkylene group with carbon atoms of 2 to 4.
  • oxyalkylene group oxyethylene group, oxypropylene group, oxybutylene group, oxyisobutylene group, and oxystyrene group may be preferably included, and oxyethylene group, oxypropylene group and oxybutylenegroup may be more preferable, and oxyethylene group and oxypropylene group may be further more preferable.
  • these oxyalkylene groups are present plurally in one constitutional unit (namely, n in the formula (2) is 2 or more), they may be present singly or in a mixed form of two or more members in one constitutional unit. In the case when two or more members of oxyalkylene groups are present, theymay take any formof a random addition, a block addition, an alternate addition, and the like.
  • At least one of OR 7 in the formula (2) is preferably represented by the following formula (3):
  • polyoxyalkylene chains represented by oxyethylene (repeated unit number: o), oxyalkylene (repeated unit number: p) and oxyethylene (repeated unit number: q), take a form of so-called a block copolymer of an A-B type or an A-B-A type.
  • a block copolymer of an A-B type or an A-B-A type can strongly express water-reducing performance, while an oxyalkylene block, a hydrophobic block, can further furnish workability. Therefore, a cement admixture containing a polycarboxylic acid-based polymer (B) having such polyoxyalkylene chains can express more superior effects.
  • R 9 represents an alkylene group with carbon atoms of 3 to 18.
  • an oxyalkylene group (OR 9 ) 2-methylethylene group (oxypropylene group), oxybutylene group, oxyisobutylene group, oxy 1-butene group, oxy 2-butene group and oxystyrene group may be preferably included, and oxypropylenegroup and oxybutylene group may be more preferable, and oxypropylene group may be further more preferable.
  • these oxyalkylene groups are present in plural in one constitutional unit (namely, p in the formula (2) is 2 or more), they may be present singly or in a mixed form of two or more members in one constitutional unit.
  • R 9 is preferably 2-methylethylene group (which precursor is generally propylene oxide) having carbon atoms
  • o and q each represent an average mole number of oxyalkylene groups added, and is in the range of 1 to 300.
  • o and q each represent an average mole number of oxyalkylene groups added and is in the range of 0 to 200, provided that when either one of o and q is 0, the other is in the range of 1 to 200. In this case, o and q over 300 would increase viscosity and may deteriorate workability.
  • the numbers, o and q may be the same or different values. When either one of o or q is 0, the other is not 0.
  • the numbers, o and q preferably are in the range of 0 to 200, more preferably 1 to 100, further preferably are 1 to 60, and most preferably are 1 to 40.
  • p represents an average mole number of oxyalkylene groups added, and is in the range of 1 to 50.
  • a p value over 50 may lower water-reducing performance, or increase hydrophobicity, and formulation in cement may bring about immiscibility with water for mixing and may deteriorate workability.
  • the number, p is preferably in the range of 1 to 20, more preferably 1 to 10, further preferably 1 to 6, and most preferably 1 to 4.
  • Total number of o, p and q, (o+p+q) is in the range of 2 to 300. The total number over 300 would increase viscosity and may deteriorate workability.
  • the total number of o, p and q, (o+p+q) is preferably in the range of 6 to 100, and more preferably 25 to 75.
  • a constitutional unit represented by the formula (2) is derived from a monomer (b) represented by the following formula (5).
  • R 5 , R 6 , R 7 , R 8 , x, y and n are as defined in the formula (2).
  • a polycarboxylic acid-based polymer (B), the other essential component according to the present invention may be any polymer as long as it has a constitutional unit represented by the formula (2), and a constitutional unit derived from a monomer having two or more carboxyl groups or salts thereof in its molecule, as is described in detail later, and a synthesis route thereof is not limited.
  • the synthesis route the following route can be used.
  • a polycarboxylic acid-based polymer (B) can be obtained by polymerization of a single or two or more monomers having a carboxyl group or the salt thereof and a polymerizable double bond in its molecule, and a single or two or more monomers (b) represented by the formula (5).
  • n of 1 to 10 in the formula (5) is preferable due to providing no decrease in slump or slump flow caused by decrease in fluidity of a cement composition over time.
  • OR 7 in the formula (5) is represented by the formula (3), a hydrophilic block strongly may express water-reducing performance, and a hydrophobic block further may furnish workability, and provide a more superior cement admixture and is thus preferable.
  • a monomer (b) represented by the formula (5) is not especially limited as long as it has a structure represented by the formula (5), and can be obtained by, for example, the addition of ethylene oxide and/or propylene oxide and/or other alkylene oxide having carbon atoms of 2 to 18, in such amount as to provide a specified repeating number, to an unsaturated alcohol or unsaturated carboxylic acid.
  • it can be obtained by an esterification reaction between an alcohol obtained by the addition of ethylene oxide in such amount as to provide a specified repeating number, to alcohols or phenols having a hydrocarbon group with carbon atoms of 1 to 20, and unsaturated carboxylic acid, or an ester exchange reaction between the alcohol and unsaturated carboxylate ester.
  • unsaturated alcohol which can be used in the method
  • vinyl alcohol, allyl alcohol, methallyl alcohol, 3-butene-1-ol, 3-methyl-3-butene-1-ol, 3-methyl-2-butene-1-ol, 2-methyl-3-butene-2-ol, 2-methyl-2-butene-1-ol, 2-methyl-3-butene-1-ol, and the like may be included.
  • unsaturated carboxylic acid acrylic acid, methacrylic acid, and the like may be included.
  • unsaturated carboxylate ester an alkyl ester of the unsaturated carboxylic acid, and the like can be' used.
  • alkylene oxide having carbon atoms of 2 to 18 ethylene oxide, propylene oxide, butylene oxide, unsaturated hydrocarbon epoxide, and the like maybe included. Ethylene oxide and/or propylene oxide are preferable.
  • alcohols or phenols having a hydrocarbon group with carbon atoms of 1 to 20 alkyl alcohols such as methanol, ethanol and butanol; alcohols having an aryl group such as benzyl alcohol; phenols such as phenol and para-methylphenol may be included.
  • Alcohols having carbon atoms of 1 to 3 such as methanol, ethanol, butanol are preferable.
  • a monomer (c) is selected from the group consisting of an acrylic acid, a methacrylic acid, and, a monovalent metal salt, a bivalent metal salt, an ammonium salt and an organic amine salt thereof, wherein the monomer (c) for forming the polymer (A) and the monomer (c) for forming the polymer (B) are the same or different; is included.
  • a polycarboxylic acid-based polymer (A), an essential component according to the present invention is preferably a polymer having a constitutional unit of the formula (1), and a constitutional unit derived from a monomer having two or more carboxyl groups or salts thereof in its molecule, and a synthesis route thereof is not limited.
  • a preferable method for producing a polycarboxylic acid-based polymer (A) relevant to the present invention is described below.
  • a monomer (a) represented by the formula (4) (hereinafter simply referred to as "monomer (a)"): and a monomer (c) the monomer (c) is selected from the group consisting of an acrylic acid, a methacrylic acid, and, a monovalent metal salt, a bivalent metal salt, an ammonium salt and an organic amine salt thereof, and optionally another monomer (hereinafter simply referred to as “monomer (d)”)
  • a polycarboxylic acid-based polymer (A) can be obtained.
  • the amount of the monomer (a) used is not especially limited as long as the amount allows to attain desired effects, and is preferably in the range of 10 to 95% by weight, more preferably 50 to 90% by weight, and further preferably 65 to 85% by weight, based on total weight of monomers to be used.
  • the amount of the monomer (c) used is also not especially limited as long as the amount allows to attain desired effects, and is preferably in the range of 5 to 90% by weight, more preferably 10 to 50% by weight, and further preferably 15 to 35% by weight, based on total weight of monomers to be used.
  • a monomer (d), other than the monomers (a) and (c) may further be used as a copolymerization component.
  • the amount of the monomer (d) used is in the range of 0 to 50% by weight based on total weight of monomers to be used.
  • the monomer (d) is also not especially limited as long as it does not inhibit effects provided by the monomers (a) and (c), and desired effects can further be furnished.
  • styrene for example, styrene, (meth)acrylic acid esters, acrylonitrile, acrylamide, (meth)allyl sulfonate, 2-(meth)acryloxyethyl sulfonate, 3-(meth)acryloxypropyl sulfonate, 3-(meth)acryloxy-2-hydroxypropyl sulfonate, 3-(meth)acryloxy-2-hydroxypropyl sulfophenyl ether, 3-(meth)acryloxy-2--hydroxypropyloxy sulfobenzoate, 4-(meth)acryloxybutyl sulfonate, (meth)acrylamidemethyl sulfonic acid, (meth)acrylamideethyl sulfonic acid, 2-methylpropanesulfonic acid (meth) acrylamide, and the like may be included.
  • the monomers (d) may be used singly or as a mixed form of two or more members.
  • the polycarboxylic acid-based polymer (A) can be obtained.
  • a polymerization method a well-known method such as aqueous polymerization, or solution polymerization such as polymerization in an organic solvent, emulsion polymerization, or mass polymerization, by using a polymerization initiator and a chain transfer agent, if necessary, can be used.
  • solution polymerization is preferable.
  • a solvent in carrying out solution polymerization for example, a single member or two or more members selected among water; lower alcohols such as methyl alcohol, ethyl alcohol and 2-propyl alcohol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane and n-hexane; ester compounds such as ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone, and the like can be used.
  • lower alcohols such as methyl alcohol, ethyl alcohol and 2-propyl alcohol
  • aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane and n-hexane
  • ester compounds such as ethyl acetate
  • ketone compounds such as acetone and methyl ethyl ketone, and the like
  • a solvent to be used in this case is not especially limited, in consideration of easiness of reaction control or little occurrence of side reactions, such an amount is preferable as to give a concentration, in a solvent, of monomer components comprising monomers (a) and (c), along with a monomer (d), if necessary, in the range of 1 to 90% by weight, more preferably 10 to 80% by weight, and most preferably 20 to 70% by weight.
  • reaction temperature is preferably in the range of 0°C to 90°C, more preferably 5°C to 60°C, and most preferably 10°C to 30°C.
  • a polymerization initiator As a polymerization initiator, well-known initiators canbe used and persulfates such as ammoniumpersulfate, sodium persulfate, and potassium persulfate; hydrogen peroxide; azo compounds such as azobis-2-methylpropionamidine hydrochloride and azobisisobutyronitrile; peroxides such as benzoyl peroxide, lauroyl peroxide and cumene hydroperoxide can be advantageously used.
  • persulfates such as ammoniumpersulfate, sodium persulfate, and potassium persulfate
  • hydrogen peroxide hydrogen peroxide
  • azo compounds such as azobis-2-methylpropionamidine hydrochloride and azobisisobutyronitrile
  • peroxides such as benzoyl peroxide, lauroyl peroxide and cumene hydroperoxide can be advantageously used.
  • An accelerator may be used in combination in the polymerization, and an accelerator which can be used in such a case is not especially limited, and, for example, reducing agents such as sodium hydrogen sulfite, sodium sulfite, Mohr salt, sodium pyrobisulfite, formaldehyde sodium sulfoxylate, ascorbic acid and erythorbic acid; and amine compounds such as ethylene diamine, disodium ethylenediaminotetraacetate, and glycin can be used.
  • reducing agents such as sodium hydrogen sulfite, sodium sulfite, Mohr salt, sodium pyrobisulfite, formaldehyde sodium sulfoxylate, ascorbic acid and erythorbic acid
  • amine compounds such as ethylene diamine, disodium ethylenediaminotetraacetate, and glycin can be used.
  • These polymerization initiators or accelerators may be used singly or as in a mixed form of two or more members, respectively.
  • a method thereof, kind or quantity of a polymerization initiator to be used, polymerization conditions, and the like are not especially limited, and well-known methods, and the like can be used.
  • a polymerization initiator peroxides such as benzoyl peroxide or lauroyl peroxide; hydroperoxide such as cumene hydroperoxide; and azo-compounds such as azobisisobutyronitrile, and the like can be used.
  • mass polymerization is carried out at a temperature in the range of 50 to 200°C, for example.
  • a chain transfer agent can also be used, if necessary, in the polymerization method, to adjust molecular weight of the resultant polymer.
  • Such a chain transfer agent is not especially limited, and well-known ones can be used singly or as in a mixed form of two or more members.
  • thiol-based chain transfer agents such as butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexylmercaptane, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate, 2-mercaptoethyl octanoate, 1,8-dimercapto-3,6-dioxaoctane, decanetrithiol and dodecylmercaptane; halides such as carbon tetrachloride, carbon tetrabromide, methylene chloride, bromoform and bromotrichloroethane;
  • hydrophobic chain transfer agents may be used singly or as in a mixed form of two or more members.
  • thiol-based chain transfer agents such as mercaptoethanol, thioglycerol, thioglycolic acid, mercatopropionic acid, 2-mercatopropionic acid, 3-mercatopropionic acid, thiomalic acid and 2-mercaptoethane sulfonic acid; primary alcohols such as 2-aminopropane-1-ol; secondary alcohols such as isopropanol; lower oxides and salts thereof such as phosphorous acid, hypophosphorous acid and salts thereof (sodium hypophosphite, potassium hypophosphite, and the like), and sulfurous acid, trioxosulfuric acid, dithionous acid, metabisulfurous acid and salts thereof (sodium sulfite, sodium bisulfite, sodium dithionite, sodium metabisulfite, potassium sulfit
  • any method such as a charging method at one time in whole amount, or a continuous charging method as by dropping and in portion-wise can be applicable, however, continuous charging is preferable.
  • a chain transfer agent may be introduced to a reactor as it is or may be mixed in advance with a monomer or a solvent.
  • the polymerization method may be carried out in a batch system or a continuous system.
  • a method for polymerization by means of sequential dropping of a polymerization initiator and a monomer to a reactor is preferable.
  • a copolymerization reaction with a monomer (c) is inhibited under acidic conditions of a system, by a side reaction.
  • major cause of making inside the reaction system acidic is present in the case , when the monomer (c) is an acidic monomer such as (meth)acrylic acid.
  • concentration of an acidic monomer has significant effects on reaction rate of a side reaction, neutralization of a part of the acidic monomer and suppression of a side reaction to accelerate an objective copolymerization of monomers (a) and (c) is desirable.
  • Neutralization degree of the acidic monomer is preferably in the range of 1 to 70% by mol, more preferably 5 to 60% by mol, and particularly preferably 10 to 50% by mol. Neutralization degree of the acidic monomer over 70% by mol would lower reactivity of the monomer (c) and may deposit many unsaturated carboxylate salts at wall surface of a container for storing the monomer (c).
  • an inorganic substance such as hydroxides and carbon salts of monovalent metal or bivalent metal; ammonia; organic amine can be used.
  • aqueous solution of hydroxides of monovalent metals such as sodium hydroxide and potassium hydroxide are preferable.
  • a polycarboxylic acid-based polymer (B), the other essential component according to the present invention is a polymer having a constitutional unit of the formula (2), and a constitutional unit derived from a monomer having two or more carboxyl groups or salts thereof in its molecule, and a synthesis route thereof is not limited.
  • a preferable method for producing a polycarboxylic acid-based polymer (B) relevant to the present invention is described below.
  • a polycarboxylic acid-based polymer (B) can be obtained.
  • the amount of the monomer (b) is not especially limited as long as the amount allows to attain desired effect, and is preferably in the range of 10 to 95% by weight, more preferably 50 to 90% by weight and further preferably 65 to 85% by weight, based on total weight of monomers to be used.
  • the amount of the monomer (c) used is also not especially limited as long as the amount allows to attain desired effects, and is preferably in the range of 5 to 90% by weight, more preferably 10 to 50% by weight, and further preferably 15 to 35% by weight, based on total weight of monomers to be used.
  • a monomer (e), other than the monomers (b) and (c), may further be used as a copolymerization component.
  • the amount of the monomer (e) used is in the range of 0 to 50% by weight, based on total weight of monomers to be used.
  • the monomer (e) is also not especially limited as long as it does not inhibit effects provided by the monomers (b) and (c), and desired effect can further be furnished.
  • modified polyethylene imine monomers such as a compound obtained by the addition of 0.5 to 10 moles of glycidyl methacrylate to 1 mol of a polyalkyleneimine alkyleneoxide adduct obtained by the addition of 1 to 20 moles of ethylene oxide (EO) per 1 equivalent weight of activated hydrogen (-NH) derived from an amino group of polyethylene imine may be included.
  • the polycarboxylic acid-based polymer (B) can be obtained.
  • a similar method as in a method for producing the polycarboxylic acid-based polymer (A) can be used.
  • the polymerization can be carried out by using a similar polymerization initiator, and a similar chain transfer agent, if necessary, and a similar solvent, as used in obtaining the polycarboxylic acid-based polymer (A).
  • the amount of a solvent used in the polymerization is not especially limited.
  • the amount of a solvent to be used in this case is not especially limited, in consideration of easiness of reaction control or little occurrence of side reactions, such an amount is preferable as to give a concentration, in a solvent, of monomer components comprising monomers (b) and (c), along with a monomer (e), if necessary, in the range of 2 to 70% by weight, and most preferably 3 to 50% by weight.
  • polymerization conditions such as polymerization temperature can be determined, as appropriate, depending on a polymerization method, a solvent, a polymerization initiator and a chain transfer agent to be used.
  • the polymerization temperature is preferably, in general, at not lower than 0°C, and preferably not higher than 150°C. More preferably, it is in a range of 40°C to 120°C, and most preferably in a range of 60°C to 80°C.
  • the polycarboxylic acid-based polymer (A) and the polycarboxylic acid-based polymer (B) obtained by the method may be used as a major component of a cement admixture, even as they are, however, if necessary, they may be used in a form of polymer salts by further neutralization with an alkaline substance.
  • an alkaline substance in this case, an inorganic salt such as a hydroxide, a chloride and a carbonate of a monovalent metal and bivalent metal; ammonia; and an organic amine may be preferably used; and hydroxides of monovalent metals, such as sodium hydroxide and potassium hydroxide can be particularly preferably used.
  • the weight average molecular weight of the polycarboxylic acid-based polymer (A) and the polycarboxylic acid-based polymer (B), as essential components according to the present invention is preferably, as weight average molecular weight (Mw) as reduced to polyethylene glycol by gel permeation chromatography (hereinafter referred to as "GPC"), in the range of 3,000 to 100,000, more preferably 5, 000 to 80, 000, and further preferably 7, 000 to 40,000.
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • Elution solution An elution solution to be obtained by dissolving 115. 6 g of sodium acetate trihydrate in a mixed solvent of 10999 g of water and 6001 g of acetonitrile, and adjusting the resultant solution at pH of 6.0 with acetic acid is used.
  • the cement admixture of the present invention preferably contains as an essential component the polycarboxylic acid-based polymer obtained by the method above. It is preferably in an aqueous solution form in view of handling. Further, other additives may be contained in the cement admixture of the present invention, or other additives can be added on mixing the present cement admixture with cement. As the other additives, well-known additives for cement can be used, for example, the following ones may be included:
  • cement additives materials
  • a cement wetting agent a thickener, a material separation reducing agent, a flocculating agent, a drying shrinkage reducing agent, a reinforcing agent, a self-leveling agent, an anticorrosion agent, a colorant, a fungicide, blast furnace slug, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, gypsum, and the like
  • These well-known cement additives (materials) may be used singly or in a combination of two or more members.
  • cement dispersing agent can be used in combination in a cement admixture of the present invention, and for example the following cement dispersing agents can be used:
  • Lignin sulfonic acid salts polyol derivatives; naphthalene sulfonic acid-formalin condensates; melamine sulfonic acid-formalin condensates; polystyrene sulfonic acid salts; amino sulfonic acids such as aminoaryl sulfonic acid-phenol-formaldehyde condensates as described in JP-A-1-113419 ; cement dispersing agents containing as an (a) component a copolymer of a polyalkylene glycol mono(meth)acrylate-based compound and a (meth)acrylic acid-based compound, and/or salts thereof, as a (b) component a copolymer of a polyalkylene glycol mono(meth)allyl ether-based compound and maleic anhydride, and/or hydrolysates thereof, and/or salts thereof, and as a (c) component a copolymer of a polyalkylene glycol
  • cement additives materials
  • a cement wetting agent a thickener
  • a material separation reducing agent a flocculating agent
  • a drying shrinkage reducing agent a reinforcing agent
  • a self-leveling agent an anticorrosion agent, a colorant, a fungicide, and the like
  • materials may be used singly or in a combination of two or more members.
  • a cement admixture of the present invention can be used by being added in a cement composition such as cement paste, mortar, concrete, and the like, similarly as in a well-known cement admixture.
  • a cement composition such as cement paste, mortar, concrete, and the like, similarly as in a well-known cement admixture.
  • it can also be applied to ultrahigh strength concrete.
  • the cement composition normally used substances such as cement, water, fine aggregate or coarse aggregate can be suitably used.
  • compositions added with fine powder such as fly ash, blast furnace slag, silica fume and limestone may be used.
  • "ultrahigh strength concrete” means one generally so called in a cement composition field, namely, such concrete whose hardened material manifests strength equivalent or higher as compared with conventional cement, even when water/cement ratio is reduced.
  • concrete having workability not to impair usual use, even when water/cement ratio is not higher than 25% by mass, further not higher than 20% by mass, in particular not higher than 18% by mass, in particular not higher than 14% by mass and in particular not higher than 12% by mass, and whose hardened material has a compression strength of not lower than 60 N/mm 2 , further not lower than 80 N/mm 2 , more further not lower than 100 N/mm 2 , particularly not lower than 120 N/mm 2 , particularly not lower than 160 N/mm 2 and particularly not lower than 200 N/mm 2 .
  • Portland cement normal, high early strength, ultra high early strength, moderate heat, sulfate resistant and each low alkali type thereof
  • various mixed cement blast furnace slag cement, silica cement, fly ash cement
  • white Portland cement alumina cement
  • ultra fast-cure cement (1 clinker fast-cure cement, 2 clinkers fast-cure cement, magnesium phosphate cement
  • grout cement oil well cement
  • low heat cement low heat type blast furnace slag cement, fly ash mixed low heat type blast furnace slag cement, Blite-rich cement
  • ultra high strength cement cement-based solidification material and eco-cement (cement produced from one or more kinds of municipal solid waste incinerated ash and sewage sludge incinerated ash as raw material)
  • eco-cement cement produced from one or more kinds of municipal solid waste incinerated ash and sewage sludge incinerated ash as raw material
  • fine powder such as blast furnace slug, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder and limestone, or gypsum may be added.
  • fine powder such as blast furnace slug, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder and limestone, or gypsum may be added.
  • fine powder such as blast furnace slug, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder and limestone, or gypsum
  • refractory aggregates such as silica-based, clay-based, zirconium-based, high alumina-based, silicon carbide-based, graphite-based, chrome-based, chrome-magnesite-based and magnesia-based materials can be used.
  • a unit water amount of 100 to 185 kg/cm 3 , a used amount of cement of 250 to 800 kg/m 3 and a water/cement ratio (mass ratio) of 0.1 to 0.7 is preferable; and a unit water amount of 120 to 175 kg/cm 3 , a used amount of cement of 270 to 800 kg/m 3 and a water/cement ratio (mass ratio) of 0.2 to 0.65 are is more preferably preferable.
  • the cement composition has a wide range from lean mix to rich mix can be used, which are effective to any of high strength concrete with high content of unit cement amount, and lean mix concrete with a unit cement amount of not higher than 300 kg/m 3 .
  • total weight of the polycarboxylic acid-based polymer (A) and the polycarboxylic acid-based polymer (B), as the essential components of the present invention is preferably not lower than 0.01% by weight and not higher than 10% by weight, based on 100% by weight of total cement weight.
  • the formulation rate below 0.01% by weight would be insufficient in view of performance, while the formulation rate over 10% by weight would be disadvantageous in view of economy.
  • the formulation rate is more preferably not lower than 0.05% by weight and not higher than 8% by weight, and further more preferably not lower than 0.1% by weight and not higher than 5% by weight.
  • the "% by weight" is a corresponding value to solid content.
  • Adduct compound of 20 moles of ethylene oxides to vinyl ether (hereinafter referred to as VE-20) was synthesized from diethyleneglycol monovinylether (DEGV) produced from CHEMIWAY Maruzen Petrochemical Co., Ltd. by a well-known method.
  • DEGV diethyleneglycol monovinylether
  • a solid content of the resulting polycarboxylic acid-based polymer (A-1) was 50%.
  • the molecular weight of this polymer was determined by GPC using a sample with concentration adjusted to 0.5% by the addition of a GPC eluting solution.
  • the peak (polymer peak) at Mp 34,560 and the peak (non-polymer peak) at Mp 1, 180 were separated by the lowest layer of the valley part formed between these two peaks. In this case, attention was paid so as that the peak at Mp 1, 180 did not include minus peak.
  • a ratio of area of the non-polymer peak/area of the polymer peak was found to be 23.5%.
  • a 30% aqueous solution of sodium hydroxide was added to adjust to a pH of 7, to obtain an aqueous solution of a polycarboxylic acid-based polymer (B-1) (a solid content concentration of 45% by weight) having weight average molecular weight of 14, 000 determined by GPC as reduced to polyethylene glycol.
  • reaction mixture was kept at 70°C for 1 hour. After cooling the solution, a 30% aqueous solution of sodium hydroxide was added to adjust to pH of 7, to obtain an aqueous solution of a polycarboxylic acid-based polymer (B-2) (a solid content concentration of 45% by weight) having weight average molecular weight of 8,500 determined by GPC as reduced to polyethylene glycol.
  • B-2 polycarboxylic acid-based polymer
  • aqueous monomer solution prepared by mixing 1076 parts of methoxypolyethylene glycol monomethacrylate (average adduct mole number of ethylene oxide: 4), 190 parts of methacrylic acid, 754.6 parts of a 43% aqueous solution of a monomer (b-2) shown in Table 1, 21.7 parts of a 48% aqueous solution of sodium hydroxide, 44.6 parts of 3-mercaptopropionic acid and 287 parts of distilled water, was dropped over 5 hours, and each of 240 parts of a 2.0% aqueous solution of hydrogen peroxide and 240 parts of a 5% aqueous solution of L-ascorbic acid was dropped over 6 hours.
  • aqueous monomer solution prepared by mixing 545.7 parts of a monomer (b-3) shown in Table 1, 108.0 parts of methacrylic acid, 11.8 parts of a 48% aqueous solution of sodium hydroxide, 9.76 parts of 3-mercaptopropionic acid and 148.
  • cement admixtures shown in Examples 1 to 3 and Comparative Example 1 concrete was blended and mixed with the following formulation, to evaluate addition amounts of a cement admixture to attain a specified slump flow value, along with slump values and slump flow values just after mixing (namely after 0 minute), 30 minutes after mixing and 60 minutes after mixing.
  • Formulation unit quantity was as follows: Water 175 kg/m 3 , cement 389 kg/m 3 , coarse aggregate 941 kg/m 3 and fine aggregate 791 kg/m 3 .
  • MA404 (produced from Pozzolith Bussan Co., Ltd.), as an antifoaming agent, was blended so as to be 0.003% based on cement weight.
  • Coarse aggregate Crushed limestone produced in Hachinohe, Aomori prefecture
  • Fine aggregate Pit sand produced in Kimitsu, Chiba prefecture
  • MA404 (produced from Pozzolith Bussan Co., Ltd.), as an antifoaming agent, was blended so as to be 0.005% based on cement weight.
  • Formulation quantity of a cement admixture based on cement weight was calculated as solid content of a cement admixture and shown in Table 4 in % (% by weight).
  • cement, fine aggregate and coarse aggregate were charged in the formulation above, into a 50 L forced mixer, and subjected to dry blending for 10 seconds and subsequent mixing by the addition of water formulated with a cement admixture, for further 120 seconds to produce concrete.
  • Example 1 0.190 22.5, 393 21.0, 315 19.5, 305 Example 2 0.205 23.0, 400 21.0, 330 19.5, 315 Example 3 0.155 23.5, 413 20.0, 315 19.0, 298 Comparative Example 1 0.165 23.0, 410 18.5, 290 13.5, 245 Comparative Example 2 0.215 22.5, 408 21.5, 320 19.0, 278 Comparative Example 3 0.300 22.5, 395 22.0, 320 19.5, 295
  • a cement admixture (2) of the present invention (Example 2) which comprises comparative cement admixtures (1) and (3) (Comparative Examples 1 and 3 respectively) in combination, shows small decrease in slump flow value at 60 minutes after mixing, even in a smaller amount of cement admixture than each the comparative cement admixtures (1) and (3) used in Comparative Examples 1 and 3. From these results, a cement admixture of the present invention is found to effectively suppress and prevent decrease in fluidity over time in a smaller amount.
  • the comparative cement admixture (1) used in Comparative Example 1 is a member of the polycarboxylic acid-based polymer (A) relevant to the present invention
  • the comparative cement admixture (3) used in Comparative Example 3 is a member of the polycarboxylic acid-based polymer (B) relevant to the present invention. From these points and the results, it is shown that the combined use of the polycarboxylic acid-based polymer (A) and the polycarboxylic acid-based polymer (B) according to the present invention can significantly suppress and prevent decrease in fluidity over time in a smaller amount than that used singly.
  • the cement admixture of the present invention has superior water-reducing performance, and at the same time, can suppress decrease in slump and slump flow caused by decrease in fluidity of a cement composition over time. Accordingly, by using the cement admixture of the present invention, a hardened cement material can efficiently be formed and produced, and thus it fulfills great role to build structure of civil engineering and construction with superior strength and durability.

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Claims (4)

  1. Zementzusatzmittel, das zwei oder mehr Bestandteile von Polymeren auf Polycarbonsäurebasis umfasst, wobei das Zementzusatzmittel mindestens ein Polymer auf Polycarbonsäurebasis (A) mit einem Baustein, der durch die folgende Formel (1) dargestellt wird:
    Figure imgb0020
     wobei R1 und R2 unabhängig für ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 30 Kohlenstoffatomen, eine Alkenylgruppe mit 1 bis 30 Kohlenstoffatomen, eine Arylgruppe mit 6 bis 12 Kohlenstoffatomen stehen; A für eine Alkylengruppe mit 1 bis 30 Kohlenstoffatomen oder eine Arylengruppe mit 6 bis 12 Kohlenstoffatomen steht; a 0 oder 1 ist; OR3 für eine Oxyalkylengruppe mit 2 bis 18 Kohlenstoffatomen steht, wobei jedes OR3 gleich oder voneinander verschieden sein kann, vorausgesetzt, dass, wenn OR3 in einer Mischform von zwei oder mehr Bestandteilen vorliegt, jedes OR3 in einer Block- oder statistischen Form zugegeben werden kann; R4 für ein Wasserstoffatom oder eine Kohlenwasserstoffgruppe mit 1 bis 30 Kohlenstoffatomen steht und m für eine durchschnittliche Molzahl von zugegebenen Oxyalkylengruppen steht und im Bereich von 1 bis 300 liegt; und
    mindestens ein Polymer auf Polycarbonsäurebasis (B) mit einem Baustein umfasst, der durch die folgende Formel (2) dargestellt wird:
    Figure imgb0021
     wobei R5 und R6 unabhängig für ein Wasserstoffatom, eine Methylgruppe stehen; x eine ganze Zahl im Bereich von 0 bis 2 ist und y 1 ist; OR7 für eine Oxyalkylengruppe mit 2 bis 18 Kohlenstoffatomen steht, wobei jedes OR7 gleich oder voneinander verschieden sein kann, vorausgesetzt, dass, wenn OR7 in einer Mischform von zwei oder mehr Bestandteilen vorliegt, jedes OR7 in einer Block- oder statistischen Form zugegeben werden kann; R8 für ein Wasserstoffatom oder eine Kohlenwasserstoffgruppe mit 1 bis 30 Kohlenstoffatomen steht und n für eine durchschnittliche Molzahl von zugegebenen Oxyalkylengruppen steht und im Bereich von 1 bis 300 liegt;
    wobei das Polymer (A) ein Copolymer eines Monomers (a), das durch die folgende Formel (4) dargestellt wird:
    Figure imgb0022
     wobei in der Formel (4) R1, R2, R3, R4, A, a und m wie in der Formel (1) definiert sind, und eines Monomers (c) ist, wobei das Monomer (c) aus der Gruppe bestehend aus einer Acrylsäure, einer Methacrylsäure und einem einwertigen Metallsalz, einem zweiwertigen Metallsalz, einem Ammoniumsalz und einem organischen Aminsalz davon ausgewählt ist;
    wobei das Polymer (B) durch Copolymerisation eines Monomers (b), das durch die folgende Formel (5) dargestellt wird:
    Figure imgb0023
     wobei in der Formel (5) R5, R6, R7, R8, x, y und n wie in der Formel (2) definiert sind, und eines Monomers (c) hergestellt wird, wobei das Monomer (c) aus der Gruppe bestehend aus einer Acrylsäure, einer Methacrylsäure und einem einwertigen Metallsalz, einem zweiwertigen Metallsalz, einem Ammoniumsalz und einem organischen Aminsalz davon ausgewählt ist;
    wobei das Monomer (c) zum Bilden des Polymers (A) und das Monomer (c) zum Bilden des Polymers (B) gleich oder verschieden sind; und
    wobei das Gewichtsverhältnis des Polymers auf Polycarbonsäurebasis (A) und des Polymers auf Polycarbonsäurebasis (B) [Gewichtsverhältnis von (A):(B)] im Bereich von 1:99 bis 99:1 liegt.
  2. Zementzusatzmittel nach Anspruch 1, wobei in der Formel (2) n im Bereich von 1 bis 10 liegt.
  3. Zementzusatzmittel nach Anspruch 1 oder 2, wobei in der Formel (2) OR7 durch die folgende Formel (3) dargestellt wird:
    Figure imgb0024
     wobei R9 für eine Alkylengruppe mit 3 bis 18 Kohlenstoffatomen steht; o und q unabhängig für eine durchschnittliche Molzahl von zugegeben Oxyalkylengruppen stehen und im Bereich von 0 bis 200 liegen, vorausgesetzt, dass, wenn eines von o oder q 0 ist, das andere im Bereich von 1 bis 200 liegt; p für eine durchschnittliche Molzahl von zugegebenen Oxyalkylengruppen steht und im Bereich von 1 bis 50 liegt und die Gesamtzahl von o, p und q (o+p+q) im Bereich von 2 bis 300 liegt.
  4. Zementzusatzmittel nach einem der Ansprüche 1 bis 3, wobei das Gewichtsverhältnis des Polymers auf Polycarbonsäurebasis (A) und des Polymers auf Polycarbonsäurebasis (B) [Gewichtsverhältnis von (A):(B)] im Bereich von 1:99 bis 90:10 liegt.
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